Process for the preparation of dyestuffs

Abstract

Dyestuffs of the formula ##STR1## in which D is the radical of an aromatic or heterocyclic diazo component and K is the radical of an aromatic or heterocyclic coupling component, or is the radical of an active methylene compound, are obtained in an ecologically advantageous manner by reacting an aromatic or heterocyclic diazo components of the formula D--NH.sub.2 and a coupling component of the formula H--K with a nitrite, for example NaNO 2 , in the presence of CO 2 at a pressure of 5-100 at. The process is suitable in particular for the preparation of concentrated dye-stuff solutions, because expensive operations, such as, for example, pressure permeation and reverse osmosis, can be omitted.

What is claimed is: 
     
       1. A process for the preparation of a dyestuff of the general formula   D--N═N--K                                              (I)     in which   D is the radical of a substituted or unsubstituted aromatic diazo component containing 6 to 10 carbon atoms or is the radical of a heterocyclic diazo component selected from the group consisting of substituted and unsubstituted, benzo-fused and non-benzo-fused thiazoles, isothiazoles, thiadiazoles, oxazoles, imidazoles and triazoles and   K is the radical of a substituted or unsubstituted aromatic coupling component containing 6 to 10 carbon atoms or   K is the radical of a heterocyclic coupling component of the formula ##STR49## in which R 12  represents methyl, phenyl, carboxamide or carboxylic alkyl esters of 1-4 C atoms, and   R 13  represents hydrogen, an amidino group or a phenyl radical which is unsubstituted or substituted by 1-3 halogens, alkyl, alkoxy, carboxyl, carboxamido, sulpho or sulphonamido groups,   A represents hydroxyl or amino   R 14  represents hydrogen, alkyl of 1-4 C atoms or phenyl,   R 15  represents hydrogen, alkyl or 1-4 C atoms or a phenyl radical which is unsubstituted or substituted by 1-3 halogens, alkyl or alkoxy radicals of 1-4 C-atoms, and   R 16  represents halogen, alkyl or alkoxy of 1-4 C atoms,   q is 0, 1 or 2,   or   HK is selected from the group consisting of 2-hydroxy-carbazole, 3-hydroxy-di-benzofurane, 5-hydroxyquinoline, 8-hydroxyquinoline, 5-hydroxyisoquinoline, 2,4-dihydroxyquinoline, 1-(m-nitrophenyl)-3-methyl-5-pyrazolone, 1-(p-nitrophenyl)-3-methyl-5-pyrazolone, 1,2,3,4-tetrahydro-6-methoxyquinoline, 1,2,3,4-tetrahydro-7-methylquinoline, 1,2,3,4-tetrahydro-1-methylquinoline, 1,2,3,4-tetrahydro- 1-(2-hydroxyethyl)quinoline, 3,4-dihydro-2H- 1,4-benzoxazine (benzomorpholine), 4-ethyl-3,4-dihydro-2H-1,4-benzoxazine, 4-(2-cyanoethyl)-3,4-dihydro-2H-1,4-benzoxazine, julolidine, 2-acetamido-thiophene, 2-benzamidothiophene, 2-dimethylaminothiazole; indazol-6-one, 1-dimethylaminomethyl-3-methylpyrazol-5-one,   or   HK is an activated methylene coupling component selected from the group consisting of β-diketones, beta-keto esters, beta-keto nitriles, anilides of cyano-acetic acid, heterocyclic beta-keto amides and β-imino amides or   K is a radical of the formula ##STR50## in which R 1  represents hydrogen or alkyl having 1-4 carbon atoms which is unsubstituted or substituted by halogen, hydroxyl, cyano, C 1  -C 4  -alkoxy, C 1  -C 4  -alkylcarbonyloxy, phenoxy, phenyl, hydroxycarbonyl or C 1  -C 4  -alkylsulphonyl,   R 2  and R 3 , independently of one another, represent methyl or ethyl and   R 4  represents hydrogen, halogen, alkyl or alkoxy having 1-4 C atoms, benzyl, benzyloxy, phenyl or phenoxy radicals each of which in turn is unsubstituted or substituted by halogen, alkyl or alkoxy of 1-4 C atoms, acetyl benzoyl or carboxylic esters having 1-4 C atoms,   m represents 1 or 2,   and as far as substituents for the substituted aromatic diazo component, the substituted heterocyclic diazo component or the substituted aromatic coupling component, are concerned, they are selected from the group consisting C 1  -C 4  -alkyl, C 6  -C 10  -aryl, C 1  -C 4  -alkoxy, C 1  -C 4  -alkoxycarbonyl, C 1  -C 4  -alkylcarbonyloxy, cyano, C 1  -C 4  -(di)alkylamino, C 1  -C 4  -(di)alkylaminocarbonyl, C 1  -C 4  -alkylcarbonyl-amino, halogen, C 1  -C 4  -alkylcarbonyl, C 1  -C 4  -alkylsulphonyl, C 1  -C 4  -(di)alkylaminosulphonyl, C 1  -C 4  -alkylsulphonylamino, C 1  -C 4  -alkoxysulphonyl, C 1  -C 4  -alkylsulphonyloxy, nitro, C 6  -C 10  -(di)arylamino, C 1  -C 4  -alkyl-C 6  -C 10  -aryl-amino, phenylsulphonyl, phenylazo, benzothiazolyl, 1,2,4-oxadiazolyl, morpholino, piperidino, piperazino, pyrrolidino, C 1  -C 4  -alkylmercapto and C 6  -C 10  -arylmercapto,   wherein substituents for the substituted aromatic diazo component or the substituted heterocyclic diazo component may optionally be hydroxy in which a diazo component of the formula   D--NH.sub.2     and a coupling component of the formula     H--K     are reacted in an aqueous medium with a nitrite selected from the group consisting of alkali nitrite, C 1  -C 5  -alkyl nitrite, glycol nitrite or polyol nitrite, at a CO 2  pressure of more than 5 bar at a temperature of 0°-125° C.     
     
     
       2. A process according to claim 1, in which the reaction is carried out during a time of 10 minutes to 24 hours. 
     
     
       3. A process according to claim 1, in which the reaction is carded out at a temperature of 0°-100° C. 
     
     
       4. A process for the preparation of the dyestuff of the formula ##STR51## in which R 1  represents hydrogen or alkyl having 1°-4 carbon atoms wherein said alkyl is unsubstituted or substituted by halogen, hydroxyl, cyano, C 1  -C 4  -alkoxy, C 1  -C 4  -alkylcarbonyloxy, phenoxy, phenyl, hydroxycarbonyl or C 1  -C 4  -alkylsulphonyl, R 2  and R 3 , independently of one another, represent methyl or ethyl,   R 4  and R 5 , independently of one another, represent hydrogen, halogen, alkyl or alkoxy having 1-4 C atoms, benzyl, benzyloxy, phenyl or phenoxy radicals wherein each of said benzyl, benzyloxy, phenyl or phenoxy radicals are unsubstituted or substituted by halogen, alkyl or alkoxy of 1-4 C atoms, acetyl, benzoyl or carboxylic ester having 1-4 C atoms or   R 5  represents phenylazo or together with the benzene ring form a tetraline, naphthalene or benzodioxane ring system and   m and n, independently of one another, represent 1 or 2,   is obtained by reacting an aromatic amine of the formula ##STR52## and a compound of the formula ##STR53## in which R 1  to R 5 , m and n have the abovementioned meaning and   R 6  and R 7 , independently of one another, represent hydrogen, alkoxy of 1-4 C atoms, phenyl, phenoxy or C 1  -C 2  -alkyl with the proviso that R 6  and R 7  together do not contain more than 2 alkyl carbon atoms,   are reacted in an aqueous medium with a nitrite selected from the group consisting of alkali nitrite, C 1  -C 5  -alkyl nitrite, glycol nitrite or polyol nitrite, in the presence of CO 2  at a pressure of 5-100 bar at a temperature of 0°-125° C.   
     
     
       5. A process according to claim 1, in which a compound of the formula ##STR54## in which R 8  represents hydrogen, halogen, alkyl, alkoxy having 1-4 C atoms, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, trialkylammonium groups, benzyl, benzyloxy, phenyloxy radicals acetyl, benzoyl, carboxylic esters having 1-4 C atoms, carboxamide, carboxyl, nitro, sulphonamide or the sulpho group, R 9  represents hydrogen, alkyl or alkoxy having 1-4 C atoms, acylamino having 1-4 C atoms, a hydroxyl or carboxyl group,   R 10  and R 11 , independently of one another, represent hydrogen or alkyl having 1-4 carbon atoms which are unsubstituted or substituted by halogen, hydroxyl, cyano, C 1  -C 4  -alkoxy, C 1  -C 4  -carbonyloxy, phenoxy or phenyl, or   R 10  and R 11  together with the nitrogen atom to which they are attached represent the remaining members of a 5- or a 6-membered heterocyclic ring which in addition to the aforesaid N atom contain no additional heteroatom or one additional hetero atom selected from the group consisting of N, O and S, or   R 10  represents a phenyl radical which in turn is unsubstituted or substituted by halogen, alkyl or alkoxy of 1-4 C atoms, and   R 11  represents a bivalent alkylene radical which forms a partially hydrogenated 5- or 6-membered heterocyclic ring which is fused with the adjacent phenyl ring to form a bicyclic structure,   o represents 1 or 2, and   p represents 1, 2 or 3,   is obtained by reacting an aromatic amine of the formula ##STR55## with an aromatic amine of the formula ##STR56## in which R 8  to R 11  and o and p have the abovementioned meaning.   
     
     
       6. A process according to claim 1, in which K represents a radical of the formula ##STR57## D represents a phenyl radical which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen, C 1  -C 4  -alkoxy, C 1  -C 4  -(di)alkylamino, C 1  -C 4  -(di)alkylaminoalkyl, C 1  -C 4  -trialkyl-ammonium, benzyl, benzyloxy, phenyloxy, acetyl, benzoyl, C 1  -C 4  -alkoxy-carbonyl, C 1  -C 4  -(di)alkylaminocarbonyl, carboxyl, nitro, C 1  -C 4  -alkylsulphonyl and sulphonic acid   or   represents a heterocyclic radical selected from the group of substituted and unsubstituted thiazoles, benzothiazoles, isothiazoles, benzoisothiazoles, triazoles, thiadiazoles, imidazoles, benzoimidazoles, oxazoles and benzoxazoles, and the substituents for the mentioned heterocyclic radicals are selected from the group consisting of C 1  -C 4  -alkyl, C 1  -C 4  -alkoxy, C 1  -C 4  -alkoxycarbonyl, C 1  -C 4  -(di)alkylamino, C 6  -C 10  -(di)arylamino and C 1  -C 4  -alkyl-C 6  -C 10  -arylamino,   R 12  represents methyl, phenyl, carboxamide or carboxylic alkyl esters of 1-4 C atoms, and   R 13  represents hydrogen, an amidino group or a phenyl radical which is unsubstituted or substituted by 1-3 halogens, alkyl, alkoxy, carboxyl, carboxamido, sulpho or sulphonamide groups, and   A represents hydroxyl or amino.   
     
     
       7. A process according to claim 1, in which a compound of the formula ##STR58## in which R 8  represents hydrogen, halogen, alkyl, alkoxy having 1-4 C atoms, aminoalkyl, (di)alkylaminoalkyl, trialkylammonium groups, benzyl, benzyloxy, phenyloxy, acetyl, benzoyl, carboxylic esters having 1-4 C atoms, carboxamide, carboxyl, nitro, sulphonamide or the sulpho group, o represents 1 or 2,   R 12  represents methyl, phenyl, carboxamide or carboxylic alkyl esters of 1-4 C atoms, and   R 13  represents hydrogen, an amidino group or a phenyl radical which is unsubstituted or substituted by 1-3 halogens, alkyl, alkoxy, carboxyl, carboxamido, sulpho or sulphonamido groups,   is obtained by reacting an aromatic amine of the formula ##STR59## with a pyrazolone compound of the formula ##STR60## in which R 12  and R 13  have the abovementioned meaning.   
     
     
       8. A process according to claim 1, in which a compound of the formula ##STR61## in which X represents the remaining members of a thiazole, benzothiazole, 1,2,4-triazole or 1,3,4-thiadiazole radical and R 9  represents hydrogen, alkyl or alkoxy having 1-4 C atoms, acylamino having 1-4 C atoms, a hydroxyl or carboxyl group,   R 10  and R 11 , independently of one another, represent hydrogen or alkyl having 1-4 carbon atoms which are unsubstituted or substituted by halogen, hydroxyl, cyano, C 1  -C 4  -alkoxy, C 1  -C 4  -carbonyloxy, phenoxy or phenyl   R 10  and R 11 , together with the nitrogen atom to which they are attached, represent the remaining members of a 5- or 6-membered heterocyclic ring which in addition to the aforesaid N atom contain no additional hetero atom or one additional hetero atom selected from the group consisting of N, O and S, or   R 10  represents a phenyl radical which is unsubstituted or substituted by halogen, alkyl or alkoxy of 1-4 C atoms, or   R 11  represents an alkylene radical which forms a partially hydrogenated 5- or 6-membered heterocyclic ring by a ring closure with the benzene ring,   p represents 1, 2 or 3,   is obtained by reacting a heterocyclic amine of the formula ##STR62## in which X has the abovementioned meaning   with an aromatic amine of the formula ##STR63## in which R 9 , R 10 , R 11  and p have the above mentioned meaning.   
     
     
       9. A process according to claim 1, in which a compound of the general formula ##STR64## in which R 14  represents hydrogen, alkyl of 1-4 C atoms or phenyl, R 15  represents hydrogen, alkyl of 1-4 C atoms or a phenyl radical which is unsubstituted or substituted by 1-3 halogens, alkyl or alkoxy radicals Of 1-4 C atoms, and   R 16  represents halogen, alkyl or alkoxy of 1-4 C atoms,   q is 0, 1 or 2, and   X represents the remaining members of a thiazole, benzothiazole, 1,2,4-triazole or 1,3,4-thiadiazole radical,   is obtained by reacting a heterocyclic amine of the formula ##STR65## with an indole compound of the formula ##STR66## in which R 14 , R 15 , R 16  and q have the abovementioned meaning.   
     
     
       10. A process according to claim 1, in which K is a radical of the formula ##STR67## in which R 1  represents hydrogen or alkyl having 1-4 carbon atoms which is unsubstituted or substituted by halogen, hydroxyl, cyano, C 1  -C 4  -alkoxy, C 1  -C 4  -alkylcarbonyloxy, phenoxy, phenyl, hydroxycarbonyl or C 1  -C 4  -alkylsulphonyl,   R 2  and R 3 , independently of one another, represent methyl or ethyl and   R 4  represents hydrogen, halogen, alkyl or alkoxy having 1-4 C atoms, benzyl, benzyloxy, phenyl or phenoxy radicals wherein said benzyl, benzyloxy, phenyl and phenyloxy are unsubstituted or substituted by halogen, alkyl or alkoxy of 1-4 C atoms, acetyl, benzoyl or carboxylic esters having 1-4 C atoms,   m represents 1 or 2,   R 9  represents hydrogen, alkyl or alkoxy having 1-4 C atoms, acylamino having 1-4 C atoms, a hydroxyl or carboxyl group,   R 10  and R 11 , independently of another, represent hydrogen or alkyl having 1-4 carbon atoms, wherein said alkyl is unsubstituted or substituted by halogen, hydroxyl, cyano, C 1  -C 4  -alkoxy, C 1  -C 4  -carbonyloxy, phenoxy or phenyl,   R 10  and R 11 , together with the nitrogen atom to which they are attached, represent the remaining members of a 5- or 6-membered heterocyclic ring which in addition to the aforesaid N atom contain no additional or one additional hetero atom selected from the group consisting of N, O and S,   or   R 10  represents a phenyl radical which is unsubstituted or substituted by halogen, alkyl or alkoxy of 1-4 C atoms, and   R 11  represents a bivalent alkylene radical which forms a partially hydrogenated 5- or 6-membered heterocyclic ring which is fused with the adjacent phenyl ring to form a bicyclic structure,   R 12  represents methyl, phenyl, carboxamide or carboxylic alkyl esters of 1-4 C atoms, and   R 13  represents hydrogen, an amidino group or a phenyl radical which is unsubstituted or substituted by 1-3 halogens, alkyl, alkoxy, carboxyl, carboxamido, sulpho or sulphonamido groups,   A represents hydroxyl or amino,   R 14  represents hydrogen, alkyl of 1-4 C atoms or phenyl,   R 15  represents hydrogen, alkyl of 1-4 C atoms or a phenyl radical which is unsubstituted or substituted by 1-3 halogens, alkyl or alkoxy radicals of 1-4 C atoms, and   R 16  represents halogen, alkyl or alkoxy of 1-4 C atoms,   q is 0, 1 or 2, and   D is a radical of the formula ##STR68## in which R 5  represents hydrogen, halogen, alkyl or alkoxy having 1-4 C atoms, benzyl, benzyloxy, phenyl or phenoxy radicals each of which is unsubstituted or substituted by halogen, alkyl or alkoxy of 1-4 C atoms, acetyl, benzoyl or carboxylic esters having 1-4 C atoms or represents phenylazo or together with the benzene ring a tetraline, naphthalene or benzodioxane ring system or represents aminoalkyl, dialkylaminoalkyl, trialkylammonium groups, acetyl, carboxylic esters having 1-4 C atoms, carboxamide, carboxyl, nitro, sulphonamide or the sulpho group,   n represents 1 or 2 and   X represents the remaining members of a thiazole, benzothiazole, 1,2,4-triazole or 1,3,4-thiadiazole radical.   
     
     
       11. A process according to claim 1, in which the reaction is carried out at 25-65 bar. 
     
     
       12. A process according to claim 1, in which the reaction is carried out at 0°-70° C. 
     
     
       13. A process according to claim 1, in which the reaction is carried out at 30°-40° C. 
     
     
       14. A process according to claim 1, in which the nitrite is sodium nitrite, potassium nitrite, methyl nitrite, isopropyl nitrite, amyl nitrite, glycol nitrite and pentaerythritol nitrite or diethylene glycol nitrite. 
     
     
       15. A process according to claim 1, in which the reaction is carried out in an aqueous medium.